JPH01315496A - Liquid detergent containing conditioning agent and large amount alkylsulfate/alkylethoxylated sulfate - Google Patents

Abstract

Disclosed are liquid detergent compositions containing from about 5% to about 40% of an alkyl sulfate or alkyl ethoxylated sulfate surfactant, or mixture thereof, and water-insoluble, amine-organic anion ion-pair conditioning particles in a liquid base. The alkyl sulfate, alkyl ethoxylated sulfate, or mixture thereof, stabilizes the conditioning particles for improved shelf-life.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to alkyl sulfate/alkyl ethoxylated sulfate surfactant components, or mixtures thereof;
and a liquid detergent composition containing an amine-organic anion ion pair complex conditioning agent.

Background of the invention
-vash) Numerous attempts have been made to formulate laundry detergent compositions with fabric conditioning benefits such as softening and antistatic properties. Attempt to incorporate cationic conditioners into anionic surfactant-based built detergent compositions using various means to overcome the natural antagonism between anionic and cationic surfactants. Attempts have been made to do so. For example, U.S. Pat. No. 3,936,537 describes organic surfactants, builders, and
) discloses a detergent composition containing a quaternary ammonium softener in combination with a poorly water-soluble dispersion inhibitor that suppresses the early dispersion of a cationic surfactant into a cleaning solution.

Even in these compositions, a small compromise between cleaning and softening effectiveness must be made.

Another approach to providing detergent compositions with softening capabilities has involved using nonionic surfactants (instead of anionic surfactants) in conjunction with cationic softeners.

Compositions of this type are known, for example, from West German Patent No. 1,220,9
No. 56 and US Pat. No. 3,607,763.

However, the detergency benefits of nonionic surfactants are inferior to those of anionic surfactants, especially when compared to alkyl sulfates and alkyl ethoxylated sulfates, which provide superior cleaning performance in liquid detergent compositions. .

European Patent Application No. 87202 filed on November 6, 1987
No. 159.7 specifies an average particle size of about 10μ to about 300μ.
Disclosed are amine-anionic compound ion pair complex particles having the following. These particles provide excellent through-the-wash conditioning without significantly compromising cleaning performance. European Patent Application No. 87202159.7 discloses that ion-pair particles made from linear alkylbenzene sulfonates of shorter alkyl chain length impart improved processing properties and improved chemical stability in liquid detergents. is further disclosed to impart a longer shelf life to the conditioning agent particles. Further improvements in the processing properties and chemical stability of amine-organic anion ion pair complex particles are provided by Debra Kaswell in the U.S. Patent Application ``Conditioning Agents Containing Amine Ion Pair Complexes and Compositions Thereof'' filed on the same day as this application. It is obtained by incorporating into particles an amount of an amine-inorganic ion pair complex as disclosed in ``Particles.'' of ion-pairing particles in liquid detergent compositions that are aggressive toward ion-pairing conditioning particles, e.g., compositions containing large amounts of anionic and nonionic surfactants, fat builders, and polar solvents. Still further improvements in stability are desirable. Also, along with excellent through-the-wash fabric conditioning,
A higher level of cleaning performance is desirable.

It is an object of the present invention to provide a liquid detergent composition that has excellent lean performance and excellent through-the-wash fabric conditioning performance. More particularly, it is an object of the present invention that the fabric conditioning agent comprises amine-organic anion ion pair complex particles and that the conditioning particles have improved stability and therefore have long-lasting properties in detergent compositions. The object of the present invention is to provide a liquid detergent composition as described above which has a shelf life of hours and exceptional cleaning performance.

SUMMARY OF THE INVENTION The present invention provides a surfactant component selected from (1) a liquid base, (2) an alkyl sulfate-containing surfactant, an alkyl ethoxylated sulfate-containing surfactant, and mixtures thereof, from 5.0% to about 40%. , and (3) water-insoluble ion-pair conditioning particles having an average diameter of about 10μ to about 500μ, the particles having the formula: , R is H or CH3, A is an alkyl sulfonate, aryl sulfonate, alkylaryl sulfonate, alkyl sulfate, dialkyl sulfosuccinate, alkyloxybenzene sulfonate, acyl isethionate, acylalkyl taurate, alkyl ethoxylated sulfate, an amine-organic anion ion pair complex having an organic anion selected from the group consisting of olefin sulfonates and mixtures of such anions.
0.061% to about 20%. The detergent composition has a pH of about 5 to about 10. In some cases, the ion-pair conditioning particles have the formula: (Each R and R2 can independently be 012-C2o alkyl or alkenyl, each R3 is H or CH3, and X is the molar ratio of the amine inorganic anion. and the valence of the inorganic anion, where X is an integer from 1 to 3)
Contains about 95%. B is an inorganic anion, such as, without limitation, sulfate (SO4-2), hydrogen sulfate (H8O4'), dihydrogen phosphate (HPO'), and dihydrogen phosphate (HPO'). and mixtures thereof, preferably sulfates or hydrogen sulfates. Incorporation of optional amine-inorganic anion ion pair complexes into conditioning particles can improve the processing properties of the particles.

The liquid composition can additionally contain other surfactants, detergency builders, chelating agents, enzymes, soil release agents, anti-redeposition agents, and other detergent ingredients useful in fabric cleaning or conditioning applications.

It has been observed that common liquid detergent ingredients, including polar solvents, surfactants, and builders, can adversely affect the stability of the amine-organic anion ion pair conditioning particles.

Surprisingly, it has now been discovered that large amounts of alkyl sulfates and alkyl ethoxylated sulfates added to liquid detergent compositions promote the stability of ion pair conditioning particles.

DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "liquid detergent composition" refers to a composition containing a liquid base, a surfactant component selected from alkyl sulfates and alkyl ethoxylated sulfates, and ion pair conditioning particles. Probably. As used herein, the term "alkyl sulfate" surfactant will specifically mean a non-ethoxylated alkyl sulfate surfactant. Liquid detergent compositions may optionally contain other surfactants and conditioning agents, and may also include builders, other cleaning agents, or other optional ingredients such as chelating agents, enzymes, soil release agents, and may contain an anti-redeposition agent. All percentages listed below to describe the amounts of particular detergent ingredients in liquid detergent compositions are defined as weight percent of the total liquid detergent composition, unless otherwise specified.

Conditioning Particles Ion Pairs Conditioning particles consist of water-insoluble particles consisting of an amine-organic anion ion pair complex and optionally an amine-inorganic anion ion pair complex.

The amine-organic anion ion pair complex has the following formula:
or CH,3). A represents an organic anion, including various anions derived from anionic surfactants and related alkyl or alkenyl short chain compounds that do not exhibit surface activity.
is alkyl sulfonate, aryl sulfonate, alkylaryl sulfonate, alkyl sulfate,
selected from the group consisting of dialkyl sulfosuccinates, alkyloxybenzene sulfonates, acyl isethionates, acylalkyl taurates, alkyl ethoxylated sulfates, and olefin sulfonates, and mixtures of such anions.

As used herein, the term alkyl sulfonate will encompass alkyl compounds having sulfonate moieties at fixed or predetermined positions along the carbon chain, as well as compounds having sulfonate moieties at random positions along the carbon chain. .

The optional amine-inorganic anion ion pair complex is of the formula:
H3, where X corresponds to the molar ratio of amine to inorganic anion and the valence of the inorganic anion, and X is an integer from 1 to 3. B is an inorganic anion, such as, but not limited to, sulfate (304-2), hydrogen sulfate (HSO4-1), nitrate (NO-), phosphate (po'), hydrogen phosphate (HPO -2), and dihydrogen phosphate (HPO'), and mixtures thereof, preferably sulfates or hydrogen sulfates.

In order for the conditioning particles of the present invention to provide fabric care benefits through cleaning, the average particle size is about 1.0 to about 5.
It was found that it should have 00μ. Preferably, the particles have an average diameter of less than about 350μ, more preferably less than about 200μ, and most preferably less than about 150μ. Also preferably, the particles have an average diameter of greater than about 40μ, more preferably greater than about 50μ; the term "average particle size" refers to the average particle size of the actual particles of a given material. means. Averages are calculated on a weight % basis. The average is determined by conventional analytical techniques, for example by laser beam diffraction or microscopic measurements utilizing a scanning electron microscope. Preferably, more than 50% by weight of the particles, more preferably more than 70% by weight, most preferably more than 90% by weight of the particles are less than about 500μ, preferably less than about 350μ, more preferably less than about 200μ. It has a measured diameter of . Also preferably, more than 50% by weight of the particles, more preferably more than 70% by weight, most preferably more than 90% by weight of the particles are larger than about 10μ;
Preferably greater than about 40 μ, more preferably about 5
It has a measured diameter greater than 0μ.

Complexation of organic and optionally inorganic anions with amines results in ion-pair entities that are chemically distinct from their respective starting materials.

In addition to the ratio of amine-organic anion ion pair complex: amine-inorganic anion ion pair complex, the type of amine,
Factors such as the type of organic or inorganic anion used, the ratio of amine to organic and inorganic anions, and whether the complex will have gelatinous (soft) or coagulating (hard) properties at a particular temperature may affect the physical properties of the resulting composite, including the thermal phase transition temperature, which affects the

These factors are detailed below.

Conditioning particles containing any ion pair complex of formula (2) preferably contain from about 5 to about 95% by weight of the particle of the amine-organic anion ion pair complex of formula (1) and from about 95 to about 5% by weight of an amine-inorganic anion ion pair complex of formula (2), more preferably from about 40 to about 90% by weight of a complex of formula (1) and from about 60 to about 10% by weight of formula (2). a composite of formula (1), preferably containing from about 50 to about 80% by weight of a composite of formula (1) and from about 50 to about 20% by weight of a composite of formula (2); In the case of highly preferred conditioning particles in which the anionic component is a C3 linear alkylbenzene sulfonate (cumene sulfonate), most preferably about 70% by weight of the formula (1
) and about 30% by weight of the complex of formula (2).

The ratio of complexes of formula (1) to complexes of formula (2) determines whether particles containing these ion-pair complexes have gelatinous (soft) or coagulated (hard) properties at a particular temperature. It may affect something. proportionally more expressions (
By incorporating the ion pair complexes of 2), the particles tend to be more coagulated (harder) and therefore easier to prill or machine into particles. By incorporating proportionally more fabric care active ion pair complexes of formula (1) into a eutectic mixture, particles made from such a eutectic mixture tend to have higher fabric care conditioning performance. Thus, the optimal fabric care conditioning agent formulation will involve a balance of these factors and will not necessarily be the same for all applications. However, such balancing can be accomplished by those skilled in the art without undue experimentation.

The starting amine for the ion pair complex of formula (1) is of the formula: (wherein each R and R2 are independently 01° to C2o alkyl or alkenyl, preferably CI6 to C2o alkyl or alkenyl, most preferably C-C alkyl, and R3 is H or 18 2G CH3. Suitable non-limiting examples of starting amines include citallowamine, citallowmethylamine, civalmitylamine, civalmitylmethylamine, distearylamine,
Distearylmethylamine, dialchydylamine, dialchydylmethylamine, valmitylstearylamine 1
, palmitylstearylmethylamine, palmitylarachidylamine, valmitylarachidylmethylamine, stearylaraxylamine, stearylaraxylmethylamine, tallow palmitylamine, tallow palmitylmethylamine, tallow stearylamine, tallow stearylmethylamine , tallow alaxylamine, and tallow alaxylmethylamine. Most preferred are cytalloamine, distearylamine, cytallomethylamine and distearylmethylamine.

Organic anions (A) useful in the ion pair complexes of the present invention include alkyl sulfonates, arylsulfonates, alkylaryl sulfonates, alkyl sulfates, alkyl ethoxylated sulfates, dialkyl sulfosuccinates, alkyloxybenzene sulfonates, acyl isethio esters, acylalkyl taurates, olefin sulfonates, and mixtures thereof.

Preferred organic anions are 01-C2o alkyl sulfonate, 01-C2o alkylaryl sulfonate,
01-C2o alkyl sulfate, 01-C2o alkyl ethoxylated sulfate, aryl sulfonate,
and dialkyl sulfosuccinates.

01~C2o alkyl ethoxylated sulfate, 01~
More preferred are C20 alkylaryl sulfonates, aryl sulfonates, and dialkyl sulfosuccinates.

01-C2o alkylaryl sulfonates and arylsulfonates are preferred, with benzene sulfonates (the benzene sulfonates used herein do not contain a hydrocarbon chain directly attached to the benzene ring) and 0
1-CI3 Linear alkylbenzene sulfonate (LAS
) are particularly preferred. The benzenesulfonate moiety of LAS can be placed on any carbon atom of the alkyl chain, and is usually on the secondary carbon atom for alkyl chains having three or more carbon atoms.

The most preferred organic anions are benzenesulfonate and C1-C5 linear alkylbenzenesulfonate (L
AS), especially C1-C3 LAS.

The organic anions are generally manufactured by commercial companies such as Aldrich Chemical Company, Inc., Milwaukee, Rice, Vista Fist Chemical φ Company, Bonnli, Oklahoma, and Leutger's Nice Chemical Company, State College, Pennsylvania. It can be obtained in acid or soluble salt form from commercial chemical suppliers. Anionic acids are preferred. The amines are manufactured by Cierex Chemical Co., Ltd. in Dublin, Ohio.
It can be obtained from the Corporation.

Citalloamine complexed with an aryl sulfonate or a 01-C2o alkylaryl sulfonate; Citallomethylamine complexed with an aryl sulfonate or a 01-C20 alkylaryl sulfonate; Ditalomethylamine complexed with an aryl sulfonate or a 01-C2o alkylaryl sulfonate stearylamine and
Complexes formed from a combination of an aryl sulfonate or a C1-C2o alkylaryl sulfonate and a complexed distearylmethylamine are preferred. Complexes formed from citallow amine, citallow methyl amine, distearyl amine or distearyl methyl amine complexed with benzene sulfonate or 01-CI3 linear alkyl benzene sulfonate (LAS) are preferred.

Ditalo complexed with benzene sulfonate or 01-05 linear alkylbenzene sulfonate.

Complexes formed from amines, sitallomethylamine, distearylamine or distearylmethylamine are preferred. Most preferred are conjugates made from cytalloamine, cytallomethylamine, distearylamine or distearylmethylamine conjugated with 01-C3LAS.

The starting amine for any ion pair complex of formula (2) is of the formula; Most preferably C-C alkyl, each R3 being H or CH3. Suitable non-limiting examples of starting amines for the complex of formula (2) include citallowamine, citallowmethylamine, civalmitylamine, civalmitylmethylamine, distearylamine, distearylmethylamine,
Diarachidylamine, diarachidylmethylamine, palmitylstearylamine, palmitylstearylmethylamine, palmitylaraxylamine, palmitylaraxylmethylamine, stearylaraxylamine, stearylaraxylmethylamine, tallow valmitylamine, tallow Examples include valmitylmethylamine, tallowstearylamine, clostearylmethylamine, tallow alaxylamine, and tallow alaxylmethylamine.

The inorganic anion component of the amine-inorganic anion ion pair complex is an inorganic acid, including, without limitation, acids with -valent, divalent, and trivalent anions, such as nitric acid, sulfuric acid, and phosphorous acid. can be obtained from. Sulfuric acid is particularly preferred.

These acids are commonly available from chemical suppliers including Aldrich Chemical Company, Inc. of Milwaukee, Wisconsin, and Sigma Chemical Company of St. Louis, Missouri.

The fabric care agent of the present invention can be comprised of particles containing both an amine-organic anion ion pair complex of Formula 1 and an amine-inorganic anion ion pair complex of Formula 2. These two types of ion pair complexes are physically brought together in such a way that particles containing said combination of ion pair complexes are formed. This can be accomplished by forming each type of ion pair complex separately and then physically combining them by mixing together 2N molten ion pair complexes. Another method of providing a mixture of two types of ion pair complexes is, for example, by combining an organic anionic component A1 an inorganic component B1 and an amine component in an amount sufficient to produce the desired amount of each type of ion pair complex. A method of cooperatively producing the above-mentioned complexes by preparing a melt containing

The amine and the organic anion have a molar ratio of amine to anionic compound of 10:1 to about 1=2, preferably about 5=1.
to about 1:2, more preferably about 2=1 to 1=2, most preferably about 1:1. Organic anion is 0
1 to CBLAS and the inorganic anion is a divalent sulfate anion, the amine and the inorganic anion are in a molar ratio of from 10:1 to about 1:2, preferably about 5:1 to about 1=2, more preferably about 3=1 to about 1:1, most preferably about 2=1
Let's do it together. The amine amounts noted in the above ratios are based on the separate preparation of the ion pair complexes of Formula 1 and Formula 2. Therefore, when producing ion pair complexes of formulas 1 and 2 cooperatively, the molar ratio of amine:organic anion:inorganic anion is adjusted to the preferred ratio of the complexes of formulas (1) and (2). It will depend. For example, Citaloamine-03LA
Weight ratio of S to Citaloamine-sulfate 70/30
Highly preferred citalohamine-03LAS for use in
/citallowamine-sulfate eutectic, the molar ratio of sitalloamine, C3LAS1, and sulfate in the starting materials would be about 5.7 to 3.7:1.

Another method for making conditioning particles involves heating the amine to a liquid state, adding the desired amount of this molten amine component to separate heated acidified aqueous solutions of organic and inorganic anions, and then using a solvent such as chloroform. This method extracts ion pair complexes by Alternatively, the molten amine can be added to a mixture of heated, acidified aqueous solutions of organic and inorganic anions, followed by solvent extraction.

The desired particle size can be determined, for example, by blending the ion-pair complex with
For example, an Oster blender] medium or large ti mill [e.g. Wiley
This can be achieved by mechanically crushing the particles in a mill to achieve the desired particle size range. Preferably, the particles are formed by prilling in a conventional manner, such as by hydraulically forcing a eutectic of the ion-pair complex through a heated nozzle. Before passing through the nozzle, the eutectic
For example, the eutectic should be kept well mixed by continuously circulating it through the loop at a rate sufficient to prevent settling. Instead of hydraulically forcing the eutectic through the nozzle, an air jet can be used to force the eutectic through the nozzle.

Particle sizes within the preferred range can be obtained directly from the prilling equipment, or when additional control of average particles is desired, such desired particle size can be obtained by conventional sieving techniques. A composite eutectic that is gelatinous (ie, soft) at room temperature can be flash-frozen, for example, by using liquid nitrogen, and then mechanically milled to achieve the desired particle size. The particles can then be formulated into a liquid delivery system, such as a detergent base, an aqueous base, etc. useful for preparing aqueous dispersions of the particles. Alternatively, the eutectic can be added to a liquid delivery system, such as a detergent base, and then formed into particles by high shear mixing.

Composites can be characterized for the purposes of the present invention by their thermal phase transition temperature. As explained below, thermal phase transition (hereinafter referred to as “
(sometimes referred to as "transition point") means the temperature at which a composite material first exhibits either softening (solid to liquid crystalline phase transition) or melting (solid to isotropic phase transition) upon heating. Will.

The transition temperature was determined by differential scanning calorimetry (DSC) and/or
Alternatively, it can be measured by polarized light microscopy. The first transition temperature of solid particles made from ion pair complexes or mixtures of ion pair complexes is preferably between about 0°C and about 10°C.
It will be 0°C, more preferably about 0°C to about 100°C, most preferably about 5°C to about 80°C.

For amine-organic anion ion pair complexes, an anion with a shorter alkyl or alkenyl chain length generally has a higher transition temperature than an otherwise identical complex with an anion with a longer chain length. will produce a complex with Highly preferred ion pairs are C1-C13
produced using LAS or benzene sulfonate;
It generally has a transition point within the range of 10°C to 100°C.

Amine-organic anion ion pair complexes produced using C6~Ct a L A S are generally heated at about 5°C.
It has a first transition temperature in the range of ~30°C and tends to be gelatinous (soft). The amine-organic anion ion pair complex produced using C LAS and benzene sulfonate (i.e., without alkyl chain) is
Eutectic amines that generally have a first transition temperature in the range of about 0°C to about 100°C and tend to be more coagulable (hard) and therefore less prone to prilling - organic anion ions There is a tendency to form pair complexes or amine-organic anion/amine-inorganic anion ion pair complexes.

Preferred conditioning particles are 01-C3L A
The amine-inorganic anion ion pair complex is prepared using an organic anion component derived from S and has a transition point away from the amine-inorganic anion ion pair complex in the range of about 35°C to about 100°C.

Preferred amine-organic anion ion pair complexes include those consisting of citallowamine, citallowmethylamine, distearylamine or distearylmethylamine complexed with C1-C3LAS in a 1:1 molar ratio. . These complexes are generally heated from about 35°C to about 1
It has a transition point of 00°C. Preferred amine-inorganic anion ion pair complexes for use in conjunction with the preferred amine-organic anion ion pair complexes include sitalloamine, sitallomethylamine, distearylamine complexed with sulfate in a 1:2 molar ratio. and distearylmethylamine.

The above temperature ranges are approximations and are not meant to exclude complexes outside the above ranges. Additionally, it should be understood that the particular amine of the ion pair complex can affect the transition point. For example, for the same anionic compound, distearylamine will produce a harder ion pair complex than sitalow amine, and sitalow amine will produce a harder ion pair complex than sitalow methylamine. will.

The ideal conditioning particles are large enough to become entrapped within the fabric during washing, and at least a substantial portion of the particles, preferably all, soften or melt at normal automatic washer/dryer temperatures. It has a transition point low enough to melt during fabric washing or rinsing steps.

Ion pair conditioning particles can be incorporated into or used in the presence of detergent compositions with little, if any, adverse effect on cleaning. These conditioning particles provide conditioning benefits across a variety of laundering conditions, including machine wash or hand wash then machine dry conditions, and machine wash or hand wash then line dry conditions. Additionally, these same conditioning agents can be used in conjunction with various surfactant systems.

Conditioning particles typically range from about 0.1% to about 20.0%, preferably 0.1% to about 20.0%, of the liquid detergent composition in which they are used or incorporated.
It is used in the present invention in amounts of 1% to about 10%. The components of the detergent composition will be described below.

Liquid Base The liquid detergent compositions of the present invention have a liquid base component that functions as a carrier and diluent for other detergent components. The liquid base is preferably water or other polar solvent, or a mixture thereof. Exemplary non-limiting polar solvents include, in addition to water, low molecular weight primary and secondary-hydric alcohols, such as methanol, ethanol, and isopropanol, and about 2 to about 6 carbon atoms and about Polyols having 2 to about 6 hydroxy groups, such as propylene glycol, ethylene glycol, glycerin,
and 1,3-propanediol. Typically, liquid detergent compositions have a liquid base of about 30% to about 80%
%, preferably from about 20% to about 7% water.
It will contain 0%.

The detergent compositions of the present invention have an alkyl sulfate/alkyl ethoxylated sulfate surfactant component as an essential element. The surfactant component can consist of an alkyl sulfate (ie, non-ethoxylated alkyl sulfate) and/or an alkyl ethoxylated sulfate surfactant. These surfactants are
Typically, the alkyl or hydroxyalkyl group has about 10 to about 20 carbon atoms and has the formula RO(CHO
) In the So Mr formula, R is a hydroxyalkyl group in which H is a C1゜24 m 3 -C alkyl or C10"C20 alkyl component, preferably a 012 -C alkyl or hydroxyalkyl, more preferably a C1
2-C15 alkyl or hydroxyalkyl,
m is from 0 (inclusive) to about 4, and M is a cation that can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted ammonium cation. I can do it. Specific examples of substituted ammonium cations include methyl-, dimethyl-1 and trimethyl-ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and ethylamine, diethylamine, triethylamine, etc. In the case of alkyl sulfates, such as those derived from alkylamines, and mixtures thereof, where the salt is preferably an olefin sulfonate having from about 12 to about 24 carbon atoms, m will be 0. . For surfactant components containing alkyl ethoxylated sulfates, m typically ranges from about 0.5 to about 4
, preferably from about 0.5 to about 3. Examples of preferred surfactants in the surfactant component are C12-01B non-ethoxylated alkyl sulfates (CE(0)M),
C12-C1G alkyl 12-16 polyethoxylate (1,0) sulfate (CE(1
,0)M), C1□~C16 alkyl 12~16 polyethoxylate (2,25) sulfate (CE
(2,25)M), CI2~018 Al I2~I
θ Kyl polyethoxylate (3,0) sulfate (C,
E (3,0)M), and C1° ~ C1[i12 1
[3 Alkyl polyethoxylate (4,0) sulfate (
CE (4,0)M), where M is selected from 12-10 thorium and potassium.

The alkyl sulfate/alkyl ethoxylated sulfate surfactant component is prepared by sulfating a non-ethoxylated linear or branched alcohol having an alkyl group of 10 to 18 carbon atoms, preferably about 12 to about 16 carbon atoms. or about 10 to about 18 carbon atoms, preferably about 1 carbon number
It can be produced by sulfating ethoxylated alcohols having from 2 to about 16 alkyl groups, or by sulfating mixtures of such non-ethoxylated alcohols and ethoxylated alcohols. Non-ethoxylated alcohols such as those described above are commonly available.

The ethoxylated alcohol is preferably produced as follows. First, the non-ethoxylated alcohol (described above) is subjected to a conventional alkaline catalyzed ethoxylation reaction to give an average of 0.5 to about 4, preferably about 0.5, per mole of alcohol.
Ethoxylate with ~3 moles of ethylene oxide. The alkyl sulfate and/or alkyl ethoxylated sulfate should be neutralized with a suitable base as a final step.

Typically, surfactant components containing alkyl ethoxylated sulfates will also contain some alkyl sulfate due to incomplete ethoxylation of the alcohol. The resulting product will also typically have a mixture of alkyl or alkyl ethoxylate chain lengths. The alkyl sulfates and/or alkyl ethoxylated sulfates of the surfactant component are water-soluble or dispersible salts, preferably sodium salts, potassium salts, ammonium salts, monoethanol ammonium salts, jetanol ammonium salts, triethanol ammonium salts, or as a magnesium salt, or a mixture thereof.

A particularly preferred anionic surfactant is a mixture of fatty alcohols having about 14 to about 15 carbon atoms and about 0% ethylene oxide.
．． The sodium salt of the sulfation reaction product with 5 to about 3.0 moles.

The liquid detergent compositions of the present invention will contain at least 5.0% to less than about 40% surfactant component, preferably less than about 25% surfactant component.

The 40% upper limit is, in part, only a practical limit for the foaming typically provided by alkyl sulfate/alkyl ethoxylated sulfate surfactants during agitation. Anti-foaming agents, detailed below, may be utilized to control sudsing and may be particularly desirable when the surfactant component content exceeds about 25%.

Anti-foaming agents Fatty acids such as hydrogenated marine oil fatty acids (mainly 018-C2o) can be used, but non-soap anti-foaming agents are preferred.

Preferred foam suppressants consist of silicones. In particular, particulate suds suppressors consisting of silicones and silanized silicas releasably encased in water-soluble or dispersible, substantially non-surface-active, detergent-impermeable carriers may be used. Foam suppressants of this type are disclosed in British Patent No. 1.407,997.

Suitable foam control products include silica/silicone (15% by weight silanized silica obtained from Dow Corning, 7% fflit% silicone), 65% sodium lipolyphosphate, tallow alcohol condensed with 25 molar proportions of ethylene oxide. 25% and 3% water. The amount of silica/silicone suds control agent used depends on the degree of suds control desired, but is often 0.01% of the detergent composition.
It is within the range of ~0.5%. Other foam suppressors that may be used are water-insoluble waxes, preferably with a melting point of 35-125°C, such as those described in British Patent No. 1,492,938.
and a microcrystalline wax having a saponification value of less than 100.

Still other suitable suds control systems are disclosed in published European Patent Application No. 0000
Mixtures of hydrocarbon oils, hydrocarbon waxes and hydrophobic silicas as described in US Pat. Particulate suds suppressing compositions consisting of such mixtures in combination with compatibilizers, such as urea. These granular antifoam compositions are described in published European patent application no. 1o008830.

Detergent Surfactant System The amount of total detergent surfactant (including alkyl sulfate and/or alkyl ethoxylated sulfate surfactants) incorporated into the detergent compositions of the present invention depends on the particular surfactant or surfactants used. It can vary from about 1% to about 98% by weight of the composition depending on the agent and desired effect. Preferably 1
All of the above detergent surfactants constitute from about 10% to about 60% by weight of the composition. In addition to the anionic alkyl sulfates and alkyl ethoxylated sulfates mentioned above as part of the essential surfactant component, combinations with anionic, cationic and nonionic surfactants can be used. The liquid detergent composition preferably contains primarily anionic surfactants or a combination of anionic and nonionic surfactants.

Preferred optional anionic surfactants for liquid detergent compositions include linear alkylbenzene sulfonates. Preferred nonionic surfactants include alkyl polyethoxylated alcohols.

Other types of surfactants can be used, such as semipolar surfactants, amphoteric surfactants, zwitterionic surfactants or cationic surfactants. Mixtures of these surfactants can also be used.

A. Additional Anionic Detergent Surfactants In keeping with the technology related to detergent surfactants, liquid detergents typically incorporate surfactants in a stable acid form.

Any anionic detergent surfactant suitable for use as a detergent surfactant in the present invention includes sulfonates, such as those commonly found in U.S. Patent No. 3,929,678, column 23, lines 58 to 29, line 23 and as disclosed in U.S. Pat. No. 4,294,710. Examples of useful anionic surfactants include the following:

1. Ordinary alkali metal soaps, e.g. about 8 to about 2 carbon atoms
4. Sodium salts, potassium salts, ammonium salts and alkylolammonium salts of higher fatty acids preferably having about 10 to about 20 carbon atoms. Preferred alkali metal soaps are
Sodium laurate, sodium stearate, sodium oleate and potassium palmitate.

2. Water-soluble salts of organic sulfuric acid reaction products having an alkyl group having about 10 to about 20 carbon atoms and a sulfonic acid ester group or a sulfuric acid ester group in the molecular structure, preferably alkali metal salts, ammonium salts and alkylolammonium salts (The term "alkyl" includes the alkyl portion of an acyl group).

Examples of this group of anionic surfactants include sodium and potassium alkylbenzene sulfonates in which the alkyl group has from about 9 to about 15 carbon atoms in a straight or branched configuration, e.g., U.S. Pat. ．．
No. 220,099 and U.S. Patent No. 2.477.
It is of the type described in the specification of No. 383. Linear straight-chain alkylbenzene sulfonates (abbreviated C11-C13L) having an average number of carbon atoms in the alkyl group from about 11 to about 13
AS) are particularly useful.

Other anionic surfactants include sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil: sodium coconut oil fatty acid monoglyceride sulfonate and sodium coconut oil fatty acid monoglyceride sulfate; Included are sodium or potassium salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl group has from about 8 to about 12 carbon atoms.

Also, α having about 6 to about 20 carbon atoms in the fatty acid group and about 1 to about 10 carbon atoms in the ester group
- water-soluble salts of esters of sulfonated fatty acids; 2-acyloxyalkanes-1- having about 2 to about 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety; Water-soluble salts of sulfonic acids; and β-alkyloxyalkane sulfonates having about 1 to about 3 carbon atoms in the alkyl group and about 8 to about 20 carbon atoms in the alkane moiety. Useful alkyl ether sulfates are described in U.S. Patent No. 4,807.21.
It is detailed in the specification of No. 9.

The surfactant preferably accounts for about 8 to about 18% of the composition.
% (by weight), more preferably from about 9 to about 14% by weight.

Preferred optional anionic surfactants for use in liquid detergent compositions are linear C11"" C13 alkylbenzene sulfonates.

3. Anionic phosphate surfactants 4. N-alkyl substituted succinamates B. Nonionic detergent surfactants Suitable nonionic detergent surfactants are generally those described in U.S. Pat. No. 3,929.678 @ column 13. Lines 14 to 16
It is disclosed in column 6. Types of useful nonionic surfactants include the following.

1. Polyethylene oxide condensate of alkylphenol. These compounds include condensates of alkylphenols having alkyl groups having from about 6 to about 12 carbon atoms in either a straight or branched configuration with ethylene oxide (ethylene oxide contains about 5 to about 50% ethylene oxide per mole of alkylphenol) present in an amount equal to 25 moles).

Examples of compounds of this type include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; Dinonylphenol condensed with ethylene oxide; and diisooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal (1g131) alTM), marketed by GAF Corporation.
CO-630, TritonTM marketed by Rohm & Haas Company
X-45, X-114, X-100, and X-1
02 is mentioned.

2. Aliphatic alcohol and ethylene oxide about 1 to about 25
Condensate with moles. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally has from about 8 to about 22 carbon atoms. Number of carbons: approx. 1
Particularly preferred are condensates of alcohols having from 0 to about 20 alkyl groups and from about 4 to about 10 moles of ethylene oxide per mole of alcohol. Examples of such ethoxylated alcohols include the condensation of myristyl alcohol with about 10 moles of ethylene oxide per mole of alcohol; and coconut alcohol (with alkyl chains varying in chain length from 10 to 14 carbon atoms); Condensation products of ethylene oxide (a mixture of fatty alcohols with ethylene oxide) and about 9 mol of ethylene oxide are mentioned.

Examples of commercially available nonionic surfactants for this scale include Tergitol" 15-S-
9 (condensation product of C1l-CI5 linear alcohol and 9 moles of ethylene oxide), Tergitol TM24-L-6
NMW (CI2~C14 second with narrow molecular weight distribution)
~condensation product of alcohol and 6 moles of ethylene oxide);
NeodolTM 45-9 (C-C
Condensate of linear alcohol and 9 moles of ethylene oxide)
, Neodol TM23-6.5 (condensate of C12-CI3 linear alcohol and 6.5 mol of ethylene oxide)
, Neodol TM45-7 (condensate of C-C linear alcohol and 7 moles of ethylene oxide), Neodol TM4
5-4 (C-C linear alcohol and ethylene oxide 4
condensate with mole), and kilo (K), marketed by The Broctor & Gamble Company.
yroTM) E OB (condensate of C13-C15 alcohol and 9 moles of ethylene oxide).

3. A condensate of ethylene oxide and a hydrophobic base produced by the condensation of propylene oxide and propylene glycol. The hydrophobic portion of these compounds has a molecular weight of approximately 1
500 to about 1800, indicating water insolubility. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid properties of the product indicate that the polyoxyethylene content is approximately 50% of the total weight of the condensate.
% (corresponding to condensation with up to about 40 moles of ethylene oxide). An example of this type of compound is Pluronic T, which is marketed by Wyandotte Chemical Corporation.
M) Those consisting of surfactants can be mentioned.

4. A condensate of ethylene oxide and the product resulting from the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylene diamine and excess propylene oxide and generally has a molecular weight of about 2500 to about 3000. This hydrophobic part is
The condensate is condensed with ethylene oxide to the extent that the condensate contains from about 40 to about 80 weight percent polyoxyethylene and has a molecular coefficient of from 5.000 to about 11.000. Examples of nonionic surfactants of this type include those comprising the TeLronic™ compound sold by Wyandotte Chemical Corporation.

5. Semipolar nonionic surfactant. Examples include one alkyl moiety of about 10 to about 18 carbon atoms and about 1 carbon atom.
A water-soluble amine oxide containing two moieties selected from the group consisting of ~3 alkyl groups and hydroxyalkyl groups; one alkyl moiety having about 10 to about 18 carbon atoms and an alkyl group having about 1 to about 3 carbon atoms. and a water-soluble phosphine oxyto containing two moieties selected from the group consisting of: Examples include water-soluble sulfoxides containing one moiety selected from the group consisting of:

Preferred semi-polar non-ionic detergent surfactants have the formula % formula % (
5) (wherein R3 is an alkyl, hydroxyalkyl, or alkylphenyl group having about 8 to about 22 carbon atoms, or a mixture thereof; R4 is an alkylene or hydroxyalkylene group having about 2 to about 3 carbon atoms, or a mixture thereof; a mixture of: X is 0 to about 3; each R5 has about 1 to about 3 carbon atoms;
3 alkyl or hydroxyalkyl groups or from about 1 to
It is an amine oxide surfactant having a dilyethylene oxide group containing about 3 ethylene oxide groups. The R5 group is
For example, they can be bonded to each other through oxygen or nitrogen atoms to form a ring structure.

Preferred amine oxide surfactants are c1o-018
alkyldimethylamine oxide and C8-C12 alkoxyethyldihydroxydiethylamine oxide.

6, a hydrophobic group having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.5 to about 10°, preferably about 1
．． Polysaccharide (e.g., polyglycoside) hydrophilic groups containing from 5 to about 3, most preferably from about 1.6 to about 2.7 sugar units; Polysaccharides. Any reducing sugar having 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moiety (in some cases hydrophobic groups are attached at the 2-, 3-, 4-, etc.-positions). to give glucose or galactose as opposed to glucoside or galactoside)
. The sugar linkage can be, for example, between position 1 of the additional sugar unit and position 2, 3, 4 and/or 6 on the previous sugar unit.

Optionally, although less desirable, there can be a polyalkylene oxide chain linking the hydrophobic and polysaccharide moieties. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated branched or unbranched alkyl groups having from about 8 to about 18 carbon atoms, preferably from about 10 to about 16 carbon atoms. Preferably,
Alkyl groups are straight chain saturated alkyl groups. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkylene oxide chain can contain up to about 10, preferably less than 5 alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-1 and hexaglucosides, galactoside, lactocyto, glucose, fructocyto, Fructose and/or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra-1 and penta-glucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.

Preferred alkyl polyglycosides have the formula (wherein R2 is alkyl, alkylphenyl, hydroxylalkyl,
hydroxyalkylphenyl, and mixtures thereof, and the alkyl group has about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2 and t is 0 to about 1
0, preferably 0; X is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2
．． 7). Glycodyl is preferably derived from glucose. To produce these compounds, first, an alcohol or alkyl polyethoxy alcohol is produced;
then reacting with glucose or a glucose source,
Generates glucoside (bonded at position 1). Additional glycosyl units can then be linked between their 1-position and the 2-, 3-, 4- and/or 6-position, preferably primarily the 2-position, of the previous glycosyl unit.

7. Fatty acid amide surfactant having the following formula [wherein R
6 is an alkyl group having about 7 to about 21 carbon atoms (preferably about 9 to about 17 carbon atoms), and each 7 is hydrogen, C-C alkyl, 0
1-C4 hydroxyalkyl, and -(C2H40)
xH, where X is about 1 to about 3] Preferred amides are C8-C2o ammonia amides,
monoethanolamide, jetanolamide, and isopropanolamide.

C0 Amphoteric Surfactants Amphoteric surfactants are those in which the aliphatic groups can be straight chain or branched, one of the aliphatic substituents has about 8 to about 18 carbon atoms, and the aliphatic substituents aliphatic derivatives of secondary or tertiary amines, or aliphatic heterocyclic secondary and tertiary amines, in which at least one of the groups contains an anionic water-solubilizing group, such as h-ruboxy, sulfonate, sulfate; It can be broadly described as a derivative. For examples of amphoteric surfactants useful in the present invention, see U.S. Pat.
See column, line 48.

D. Zwitterionic Surfactants Zwitterionic surfactants are derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium, quaternary phosphonium or It can be broadly described as a derivative of a tertiary sulfonium compound. For examples of zwitterionic surfactants useful in the present invention, see U.S. Pat.
See column, line 48.

E. Cationic Surfactants Cationic surfactants are the least preferred detergent surfactants useful in the detergent compositions of this invention.

Cationic surfactants consist of a variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally a quaternary nitrogen associated with an acid group. Pentavalent nitrogen ring compounds also
It is considered to be a quaternary nitrogen compound. Suitable anions are halides, methyl sulphates and hydroxides. Tertiary amines can have properties similar to cationic surfactants at wash solution pH values below about 8.5.

Suitable cationic surfactants include quaternary ammonium surfactants having the following formula:

tR2(OR3), ]fRq(OR3), ]2R5N”
X- [wherein R2 is an alkyl or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain; each R is independently -CH2CH2-2-CHCH(C
H3)-1 -CH2CH(CH20H)-1 and -CH2CH2
selected from the group consisting of CH2-; each R is independently 01-C
selected from the group consisting of 4 alkyl, 01-C4 hydroxyalkyl, benzyl, a ring structure formed by joining two R4 groups, a hexose polymer having less than 1000) and hydrogen (when y is not O) R5 is the same as R4 or is an alkyl chain, and the total number of carbon atoms in R2+R5 is about 18 or less; each y is from 0 to about 10
and the sum of the y values is from O to about 15; It is a mono-long chain alkyl surfactant according to the above formula. The most preferred quaternary ammonium surfactants are 08-C16 alkyltrimethylammonium,
The chlorides, bromides and methyl sulfates of C8-C1B alkyldi(hydroxyethyl)methylammonium, 08-C16 alkylhydroxyethyldimethylammonium, and 08-016 alkyloxypropyltrimethylammonium. Of the above, decyltrimethylammonium methylsulfate, lauryltrimethylammonium chloride, myristyltrimethylammonium bromide and coconut trimethylammonium chloride and coconut trimethylammonium methylsulfate are particularly preferred.

A more complete disclosure of these and other cationic surfactants useful in the present invention is found in U.S. Pat.
, 228.044.

Detergent Builders The detergent compositions of the present invention optionally contain inorganic and/or organic detergent builders to aid in mineral hardness control. These builders range from about 0 to about 80% of the composition.
% by weight, preferably from about 5 to about 50% by weight, more preferably from about 5 to about 30% by weight of detersive builder.

Water-soluble organic builders used in liquid detergent compositions include:
Mention may be made of polyacetates, polycarboxylates and polyhydroxysulfonates of carboxylic acids, alkali metals, ammonium and substituted ammoniums. Useful monocarboxylic fatty acids include Cl0=C1B alkyl monocarboxylic acids (fatty acids) and salts thereof. These fatty acids can be derived from animal and vegetable oils such as tallow, coconut oil, palm oil and palm kernel oil. Suitable saturated fatty acids can also be produced synthetically (e.g. by oxidation of petroleum or by Fischer
by hydrogenation of carbon monoxide by the Tropsch process). In addition, examples of suitable saturated fatty acids include capric fatty acids,
mW of lauric and myristic fatty acids, and mixtures thereof, e.g. lauric acid versus myristic acid
Mention may be made of ratios of about 5:1 to about 1=1 (preferably about 3=1). Unsaturated fatty acids, such as oleic acid, also
It can be added to such saturated fatty acids. Particularly preferred C1o~
C18 alkyl monocarboxylic acids are saturated coconut fatty acids, palm kernel fatty acids, and mixtures thereof.

When present, fatty acids typically make up about 0.5% to about 20% based on the total composition, preferably saturated C1
Consists of o to C14 fatty acids. Most preferably C1o
The weight ratio of -01° fatty acids to C14 fatty acids is preferably at least 1:1.

Examples of polyacetate and polycarboxylate builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and sodium, potassium, lithium, ammonium and substituted ammonium salts of citric acid. be. Citrate (preferably in the form of an alkali metal or alkanol ammonium salt) is generally added to the composition as citric acid, but can be added in fully neutralized form.

A highly preferred polycarboxylate builder is disclosed in US Pat. No. 3,308,067.

Such materials include water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, and the like.

Other builders include carboxylated carbohydrates as disclosed in US Pat. No. 3,723,322.

A class of useful phosphorus-free detersive building materials has been found to be the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergency builders.

Examples of useful ether polycarboxylates include oxydisuccinates as disclosed in US Pat. No. 3,128,287 and US Pat. No. 3,635,830.

Particular types of ether polycarboxylates useful as builders in this invention include -Fukudai (where A is H or O
B is H or , and X is H or a salt-forming cation). For example, if A and B are both H in the above formula, then the compound is oxydisuccinic acid and its water-soluble salt. A is O
If H, B are H, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. A is H
If SB is of the formula, then the compound is tartrate disuccinic acid (T
DS) and its water-soluble salts. Mixtures of these builders are particularly preferred for use in the present invention. TMS
Weight ratio of TDS to TMS of about 9723 to about 20 = 80
Particularly preferred are mixtures of and TDs. These builders are disclosed in US Pat. No. 4,663,071.

In addition, suitable ether polycarboxylates include:
Cyclic compounds, especially alicyclic compounds, such as U.S. Pat.
, 923.679 specification, 3.835,163 M8s 4.158,635 specification, 4.120,874 specification, and 4.102.9
Examples include those described in the specification of No. 03.

Other useful detergency builders include the structure [where M is hydrogen or a cation (the resulting salt is water soluble), preferably an alkali metal, ammonium or substituted ammonium cation, and n is from about 2 to about 15 (preferably n is about 2 to about 10, more preferably n is on average about 2 to about 4), and each R is the same or different, hydrogen, C alkyl
4 or C-substituted alkyl (preferably R is hydrogen).

3,3-dicarboxy-4-oxa-1.6-hexanedioate and related compounds disclosed in U.S. Pat. No. 4,566.984 are also suitable in the detergent compositions of the present invention. Other useful builders include C5-C2
o Alkyl succinic acids and their salts. A particularly preferred compound of this type is theal dodecenylsuccinate.

Also useful builders include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate. , water-soluble polyacrylate (e.g., molecular weight 2,000 to about 2
00.000), and salts of copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are U.S. Pat.
44,226. These polyacetal carboxylates can be produced as follows. The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylic esters are then attached to chemically stable end groups to stabilize the polyacetal carboxylates against rapid depolymerization in alkaline solutions, converting them to the corresponding salts, and making them surface active. Add to the medicine.

Useful builders also include kylsuccinate, a derivative of succinic acid (in the formula R
is a hydrocarbon, such as a C1o7C2o alkyl or alkenyl, preferably CI2-C10 or R may be substituted with a phodroxyl, sulfo, sulfoxy or sulfone substituent as described in said patents).

Succinate builders are preferably used in the form of water-soluble salts, such as sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.

Other useful detersive builder materials are the "one-piece builder" compositions disclosed in Belgian patent 'WS 798.856. Specific examples of such seeded builder mixtures are: 3:1 wt mixture of sodium carbonate and calcium carbonate with particle size 5μ; 2.7:1 wt mixture of sodium sesquicarbonate and calcium carbonate with particle size 0.5μ; A 20:1 wt mixture of sodium sesquicarbonate and calcium hydroxide with a particle size of 0.01μ; and a 3:3:1 wt mixture of sodium carbonate, sodium aluminate and calcium oxide with a particle size of 5μ.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron/manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof as defined below. Without being limited by theory, it is speculated that the benefits of these materials are due, in part, to their exceptional ability to remove iron and manganese ions from the cleaning solution through the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents in compositions of the invention include one or more (preferably at least two)
) units in which M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and X is from 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Aminocarboxylates that can be used include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal salts, Included are ammonium salts, and substituted ammonium salts and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least small amounts of total phosphorus are allowed in the detergent composition, and are suitable for use as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent composition. where M is hydrogen, alkali metal, ammonium or substituted ammonium, and X is 1 to about 3, preferably 1
Compounds having the following are useful, examples of which include ethylenediaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetriaminepentakis (methylene phosphonate). Preferably, these aminophosphonates are
Contains no alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally substituted aromatic chelators are also useful in the present compositions. These substances consist of compounds having the formula (wherein at least one R is -5O3H or -COOH) or their soluble salts and mixtures thereof. U.S. Pat. No. 3,812,044 discloses polyfunctionally substituted aromatic chelating/sequestering agents.

Preferred compounds of this type in acid form are in particular dihydroxydisulfobenzene and 1,2-dihydroxy-3,5
- disulfobenzene or other disulfonated catechols. Alkaline detergent compositions can contain these substances in the form of alkali metal salts, ammonium salts or substituted ammonium salts (eg mono- or triethanolamine salts).

If utilized, these chelating agents will generally constitute from about 0.1 to about 10% by weight of the detergent compositions of the present invention. More preferably, the chelating agent will constitute from about 0.1% to about 3.0% of such compositions.

Soil Release Agents Polymeric soil release agents useful in the present invention include cellulosic derivatives such as hydroxyether cellulose-based polymers, copolymer blocks of ethylene terephthalate and polyethylene oxide terephthalate or polypropylene oxide terephthalate, and cationic guar gums. Examples include.

Cellulose-based derivatives that function as soil release agents are commercially available, examples include Methoce.
Hydroxyethers of cellulose and polymers such as (Dow) JR-124
R, JR-400R.

Examples include cationic cellulose ether derivatives such as JR-30MR (Union Carbide).

See also US Pat. No. 3,928,213.

Other effective soil release agents include Jag
uar Plau R), (Stein Hall),
Cationic guar gum such as Gcndrivc 458 R (General Mills).

Preferred cellulosic soil release agents for use in the present invention are selected from the group consisting of methylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, or mixtures thereof (said cellulosic polymers have a viscosity of 15-75.00
0 centipoise).

A more preferred soil release agent is a random block copolymer of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers contain ethylene terephthalate units paired with P
It consists of repeating units of ethylene terephthalate and PEO terephthalate in a molar ratio of 25:75 to about 35:65 of EO terephthalate units (the PEO terephthalate units containing polyethylene oxide having a molecular weight of about 300 to about 2000). The molecular weight of the polymeric soil release agent ranges from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230. U.S. Patent No. 3.893 disclosing similar copolymers.
．．・See also specification No. 929. Surprisingly, these polymeric soil release agents have been found to balance the distribution of the fabric care agents of the present invention on a wide variety of synthetic fabrics such as polyester, nylon, polycotton blends, acrylics, and the like. This more uniform distribution of fabric care agents can result in improved fabric care quality.

Another preferred polymeric soil release agent has an average molecular weight of 300 to
a crystalline polyester having repeating units of ethylene terephthalate units containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units derived from polyoxyethylene glycol of 5,000; The molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystalline polymer compound is from 2:1 to 6:
It is 1. Examples of this polymer include the commercially available materials Zelcon® 5126 (manufactured by Typon) and Millise (M[1ease®) T (manufactured by ICI).

The polymer and its method of preparation are described in European Patent Application No. 185.
It is detailed in the specification of No. 417.

If utilized, these soil release agents will generally constitute from about 0.01 to about 5.0% by weight of the detergent compositions of the present invention, and more preferably, the soil release agents are
It will constitute from about 0.2 to about 3.0% by weight of such compositions.

Clay Stain Removal/Anti-Redeposition Agents The detergent compositions of the present invention may also optionally contain water-soluble ethoxylated amines that have clay stain removal and anti-redeposition properties. The liquid detergent composition preferably contains about 0.01% to about 5% water-soluble ethoxylated amine. These compounds are selected from the group consisting of:

(1) Ethoxylated monoamine having the formula (% formula %) (2) Ethoxylated diamine having the formula (XL-) 2-N-R-N-(R) (3) Ethoxylated polyamine having the formula ( 4) - ethoxylated amine polymers having a uniformity, and (5) mixtures thereof [wherein A1 is or 10-; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2 ~C12
alkylene, hydroxyalkylene, alkenylene, arylene or alkaline, or a 02-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no 0-N bond is formed; each R2
is C0-C4 or hydroxyalkyl, moiety -L-X
or the two R2 together form the moiety -(CH2)r, -
A2- (CH) - (wherein A2 is 10- or S or -CH2-1r is 1 or 2, S is 1 or 2, r
+s is 3 or 4); X is a nonionic group, an anionic group, or a mixture thereof; R3 is a substituted 03-C12 alkyl group having a p-substitution site, a hydroxyalkylene group, an alkenylene group, an aryl group, or is an alkaryl group; R4 is an 01-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkali-lene, or a 02-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units with the proviso that the O-0 bond or no O-N bond is formed; L is the polyoxyalkylene moiety -((R50) (CHCHO))-(2m
22n, R5 is 03-C4 alkylene or hydroxyalkylene, m and n are moieties -(CH2CH20)
. - is at least about 5 of said polyoxyalkylene moieties
in the case of the monoamines, m is from 0 to about 4 and n is at least about 12; in the case of the diamines, m is from 0 to about 4; about 3, and n is at least about 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R1 is other than 02-C3 alkylene, hydroxyalkylene, or alkenylene; For amine polymers, m is 0 to about 10; n is at least about 3; p is 3 to 8; q is 1 or 0; t is 1 or 0-; where t is 1 when q is 1; W is 1 or 0; x+y+z is at least 2; y+z is at least 2. The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylene. It's pentimene. Exemplary ethoxylated amines are further described in US Pat. No. 4,597,898. Another group of preferred clay stain removal/anti-redeposition agents are the cationic compounds disclosed in European Patent Application No. 111.965. Other clay stain removal/anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in European Patent Application No. 111,984; European Patent Application No. 112.
592; and the amine oxides disclosed in U.S. Pat. No. 4,548,744.

Stain release agents, such as those disclosed in the art for solely reducing stains on polyester fabrics, may also be used in the compositions of the present invention. US Pat. No. 3,962,152 discloses copolymers of ethylene terephthalate and polyethylene oxide terephthalate as soil release agents.

US Patent No. 4,174,305 discloses cellulose ether soil release agents.

Enzymes Enzymes are optional ingredients generally present at about 0.025% to about 2%, preferably about 0.05% to about 1.5% of the total composition. Preferred proteolytic enzymes have a proteolytic activity of at least about 5 Anson units [
Approximately 1,000,000 Delft units/
1, preferably from about 15 to about 70 Anson units/II, and most preferably from about 20 to about 40 Anson units/g. Proteolytic activity 0.01 to about 0.05
Anson units/g of product are preferred. Other enzymes, including amylolytic enzymes, are also desirably included in the composition.

Suitable proteolytic enzymes include many known to be suitable for use in detergent compositions. Commercially available enzyme preparations such as “Savinase T” sold by Novo Industries
M) J and “AlcalaseTM
) J. and Dast-Brokers, Delft, Netherlands.
aseTM) J h<, preferred theal. Other preferred enzyme compositions include Esperase, manufactured and sold by Novo Industries A/S of Copenhagen, Denmark, under the trade name 5p-72[rEsperase.
TM)' commercially available products, manufactured and sold by Dust Brokers of Delft, Netherlands, rAZ-
ProteaseTM.

can be mentioned.

A suitable amylase is RapldascTM, sold by Dust Procars.
) J and Novo Industries.
can be mentioned.

Suitable enzymes are further disclosed in US Pat. No. 4,101.457 and US Pat. No. 4,507.219.

Stabilizing System Preferably, the liquid detergent compositions of the present invention contain a stabilizer to maintain the fabric care agent uniformly dispersed in the liquid medium. Otherwise, density differences between the insoluble particles and the liquid-based detergent may cause final particle settling or creaming.

The choice of stabilizer for the present compositions will depend on factors such as the type and amount of solvent components in the composition.

Suitable suspending agents include various clay materials such as montmorillonite clay, quaternized montmorillonite clay (e.g., Benione™ 14, available from NL Industries), hectorite (e.g., Laponite, available from Laporte). (Lap
onlte”) S), polysaccharide gums (e.g. Merck & Co.
Kelco of Endo Company, Inc.
Xanthan gum (available from Davidson), any of several long chain acyl derivative substances, or mixtures of such substances, jetanolamide of long chain fatty acids (e.g. P
EG3 lauramide), block polymers of ethylene oxide and propylene oxide [e.g. Pluronic TMF provided by BASF Wyandotte
88], sodium chloride, ammonium xylene sulfonate, sodium sulfate, and polyvinyl alcohol. Other suspending agents found to be useful include carbon atoms from about 16 to about 22 carbon atoms, preferably about 16 carbon atoms.
It is an alkanolamide of ~18 fatty acids. Preferred alkanolamides are stearic acid monoethanolamide, stearic acid jetanolamide, stearic acid monoisopropanolamide and stearic acid monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain alkanolamides (eg, stearamide DEA distearate, stearamide MEA stearate).

The most preferred suspending agents for use in this invention are quaternized montmorillonite and hectorite clays.

The suspending agent preferably ranges from about 0.1% to about 10%.
Present in an amount of 0%, preferably about 0.5% to about 3.0%.

Other optional detergent ingredients may be used in the detergent compositions of the present invention as established in the art.
Other optional ingredients that can be included in the amount (generally 0 to about 20%) include solvents, hydrotropes, solubilizers, processing aids,
Soil precipitants, corrosion inhibitors, dyes, fillers, optical brighteners, disinfectants, pH regulators (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzyme stabilizers, bleaching agents, bleach activators, Examples include fragrances.

Product Formulation The liquid detergent composition of the present invention comprises a liquid base as described above. Liquid detergent compositions preferably contain from about 0.1% to about 20% (by weight of the total composition) of ion pair conditioning agent particles, and at least 5% of the total composition for practical reasons related to controlling excessive sudsing. It further comprises a total amount of alkyl sulfate/alkyl ethoxylated sulfate surfactant component of 0% (by weight), preferably less than about 40%, more preferably less than about 25%.

The proportions of water and other solvents in the composition will be determined, in part, by the resulting state of the fabric care agent. At room temperature, the conditioning particles should be substantially insoluble in the product and within the particle size specifications set forth above. Also, in preferred formulations of the invention, the product is desirably free-flowing over a reasonable temperature range that encompasses the specific conditions of storage and use.

The amount of the essential alkyl sulfate/alkyl ethoxylated sulfate ethoxylated sulfate surfactant component effective to enhance the stability of the conditioning particles is determined by the amount of essential alkyl sulfate/alkyl ethoxylated sulfate ethoxylated sulfate surfactant component in the conditioning particles, liquid base (particularly if a non-aqueous solvent is used), alkyl sulfate/ It depends on the particular type and/or concentration of the alkyl ethoxylated sulfate surfactant component, and the builder and other surfactants, if present. Other components not specified here may also affect the stability of the ion pair conditioning particles.

Sulfonate surfactants, such as fatty acid builders and linear alkylbenzene sulfonate surfactants, are used in conjunction with fatty acid builders, nonionic surfactants such as alkyl polyethoxylated alcohols, and polar solvents such as monohydric alcohols to form liquid detergent compositions. It is particularly aggressive towards the conditioning particles inside. Therefore, when formulating these aggressive detergent ingredients into detergent compositions, in order to achieve significant stability benefits to the conditioning particles,
Higher concentrations of alkyl sulfate/alkyl ethoxylated sulfate surfactant components will generally be required than when such aggressive detergent components are not present in the detergent composition. When significant amounts of such aggressive ingredients are present in the detergent composition, typically 7.0% or more of the detergent composition should be the alkyl sulfate/alkyl ethoxylated sulfate surfactant component.

The pH of the liquid detergent composition is about 5 to about 10, preferably about 5 to about 9. The lower limit is suggested for practical reasons related to the cleaning performance of laundry ingredients commonly used in liquid laundry detergents and the negative effects of excessively low pH on many textile materials. However, since pH higher than 10 tends to have an unduly negative effect on the chemical stability of one or more ion pair complex components of the conditioning particles, pH
should be less than about 10. By way of explanation and without being limited by theory, it is assumed that such high pH deprotonates the protons bound on the amines of the ion-pair complexes, thereby disrupting the ionic bonds necessary for the continuity of the complexed ions. .

Other optional ingredients of the liquid detergent composition include, without limitation:
Colorants, fragrances, bacterial inhibitors, optical brighteners, opacifiers, viscosity modifiers, fabric absorption enhancers, emulsifiers, stabilizers, shrinkage control agents, spotting agents, bactericides, fungicides, anticorrosive agents, etc. can be mentioned.

One preferred method of making a stable one-phase liquid detergent composition comprises: 1
It is disclosed in US Pat. In general, this U.S. patent application describes alkyl sulfate and/or alkyl ethoxylated sulfate anionic surfactants;
By condensing conditioning particles of the invention; cumene, xylene or toluene sulfonate surfactants, or mixtures thereof; smectite-type clay softeners; and ethylene oxide with straight or branched alkyl chains of 8 to 16 carbon atoms. A method for making a stable monomer liquid detergent composition containing a non-ionic surfactant (non-ionic surfactant having an HLB of about 8 to about 15) is disclosed.

Stable liquid detergent compositions are said to be obtained by incorporating the clay into the liquid base at high shear rates, for example, by mixing in a homogenizer at about 150,000 seconds. A suitable homogenizer is available from APV Gaulin, Inc. of Everett, Massachusetts.

The liquid detergent compositions of the present invention also include a liquid base, conditioning particles, and an alkyl sulfate/alkyl ethoxylated sulfate surfactant component (with or without other detergents) encapsulated in a laundry article that releases the liquid detergent composition into water. May be suitable for through-the-wash laundry articles containing fabric care or other laundry active ingredients.

These laundry articles include soluble laundry products, e.g.
Examples include dissolvable pouches.

The conditioning agent particles used in the present invention are 198
In addition to one or more ion pair complexes, non-silicone waxes may be included as disclosed in U.S. Pat.

particles comprising an amine-organic anion ion pair complex and optionally an amine-inorganic anion ion pair complex and a non-silicone wax are mixed with the components in molten form;
The particles can then be formed by forming particles according to the method described above (the method is not exclusive of other methods of producing particles comprising the components). Exemplary non-silicone waxes include hydrocarbon waxes such as paraffin wax and microcrystalline wax. The weight ratio of one or more ions to the complex birow is preferably from about 1:10 to about 10:1.

In an aspect of the laundry method of the present invention, a typical laundry cleaning aqueous solution contains from 0.1% to about 2% by weight of the detergent composition of the present invention. Fabrics to be laundered are agitated in these solutions to achieve cleaning, stain removal, and fabric care benefits.

A useful method for determining an effective amount of an alkyl sulfate/alkyl ethoxylated sulfate surfactant component to stabilize conditioning particles in a liquid detergent composition is to wash the composition in cold water after aging at a high temperature. The antistatic performance of the conditioning particles under load is measured and this performance is then compared to a control composition (otherwise substantially the same components) free of alkyl sulfates/alkyl ethoxylated sulfates after aging in a similar manner to such control compositions. This is a method of comparison.

The detergent compositions of the present invention will provide a statistically significant reduction in static electricity compared to control compositions. Preferably, the detergent composition containing the alkyl sulfate/alkyl ethoxylated sulfate surfactant component and the control detergent composition are incubated at 90° C. (about 32.2° C.) for 7 days.
Preferably, after aging for 28 days, the static charge in the wash load is approximately 4096% of the static charge in the control wash load.
A sufficient amount of the alkyl sulfate/alkyl ethoxylated sulfate surfactant component is included in the composition such that the alkyl sulfate/alkyl ethoxylated sulfate surfactant component is reduced to less than 2,596, preferably less than about 2,596.

Static electricity on a wash load can be measured by measuring the charge on the wash load upon completion of the automatic washer dryer stage.

Electrical CI can be measured using a Faraday cage, a measurement device known in the art. The total charge should be determined by summing the difference in charge determined by ML at the time of removal of each fabric piece from the wash load until all of the fabric pieces have been removed from the Faraday cage.

The wash loads for the control and test compositions should be dried under substantially equal conditions.

A conventional automatic dryer temperature range, typically about 110F (about 43.3C) to about 180F (about 82.2C), is preferred. Additionally, the automatic dryer is desirably located in an environment having a constant relative humidity, preferably about 20% to about 25% relative humidity at about 70° C. (about 21.1° C.).

The amount of liquid detergent utilized will depend on the load size, detergent strength, and degree of cleaning performance desired, and should be the same for the control and test loads. Also, the wash loads for the control and test detergent compositions should be the same with respect to the type of fabric involved. A significant number of textile articles should typically include textile materials that become electrically charged when dried by an automatic washer/dryer. Preferably, a mix of fabrics including at least cotton, polyester, acrylic and nylon is used. The detergent dosage per laundry load should be determined in harmony with the dosages acceptable for laundry detergent use in laundry detergent technology.

The liquid detergent compositions of the present invention are particularly suitable for laundry applications, but are also suitable for other applications, such as hair conditioning shampoos.

The foregoing description fully explains the nature of the invention. The following examples are presented for the purpose of illustrating the invention.

The scope of the invention should be determined by the claims that follow.

All parts, percentages and ratios used herein are by weight unless otherwise specified.

EXAMPLES The following examples illustrate the invention. The scope of the invention should be defined by the claims. The abbreviations used are:
They are as follows: C13HLAS: C13 linear alkylbenzenesulfonic acid CH,4HL AS: C11,4 linear alkylbenzenesulfonic acid Nl23-6.5T Nizier to Neodol 23-6.
C alkyl 12-13 polyethoxylate (6,5T) available as 5T. Removed T-lower ethoxylated fraction and fatty alcohol Stabilizer: Bentone 14 quaternized montmorillonite clay obtained from NL Industries DTPA Sodium diethylenetriaminepentaacetate PPT: Poly(terephthalate propylene glycol ethoxylated with about 30 moles of ethylene oxide) ester) T E P A-E t 5-18: Tetraethylenepentimene ethoxylated with 15-18 moles (average) of ethylene oxide at each hydrogen site on each nitrogen DTA Niditallowamine DSA Nidistearylamine C3Lp-s; C3ttA-type alkylbenzene sulfonate (cumene sulfonate) S04: Sulfate Miscellaneous components: Enzymes, enzyme stabilizers, other phase stabilizers, 6 ingredients, brighteners, dyes, water, other solvents, pH: A moderators' (e.g.
Monoethanolamine, jetanolamine, triethanolamine, KOH.

EXAMPLE 1 This example includes a citallowamine-linear C3 alkylbebenzene sulfonate (C3LAS) ion pair complex and a citallowamine-sulfate. We demonstrate the synthesis and generation of conditioning particles made from combination with ion-pair complexes.

Citaloamine-03LAS ion pair complex was prepared using a 1:1 molar ratio of Citaloamine (Adogen, available from Cielex Corporation, Dublin, Ohio).
R) 240) and cumene sulfonic acid. The acid is slowly added to the 70°C to 150°C melt of the amine under stirring to give a homogeneous fluid.

Distearylamine complexed with C3LAS (this amine is also available from Cielex Corporation)
can be produced by substantially the same method. This complex can then be prilled directly to form particles or mixed with the cytalloamine sulfate ion pair complex produced as described below.

The citaloamine-sulfate ion pair complex is produced by combining citaloamine and sulfuric acid in a 2:1 molar ratio. 70°C to 15°C of amine under stirring with acid
Add slowly to the 0° C. melt to give a homogeneous fluid.

Next, the citaloamine-C3LAS complex and the citaloamine-sulfate complex were each mixed at a weight ratio of 70.
: Mix together at 30. The ion pair complex or mixture of ion pair complexes is kept well mixed by circulation and hydraulically forced through a heated nozzle to form particles of the complex having an average diameter of about 50 to about 200 microns. Alternatively, the eutectic can be forced through the nozzle by an air jet.

This method of synthesis and generation of Citaloamine-03LAS particles and Citaloamine-C3LAS/Citaloamine-sulfate conditioning particles also applies to other amine-organic anionic conditioning particles, such as distearylamine-03LAS particles, and other amine-organic Anion/Amine - Inorganic anion ion pair conditioning particles can be used to produce combinations such as, but not limited to, shown below.

The amine-organic anion:amine-inorganic anion ion pair complex ratio may be within the range of about 95=5 to about 5=95, preferably in other ratios within the range of about 40:60 to about 90:10. It can be fixed.

These particles form particles as described above and then
It can be used as disclosed in the examples below by mixing with suitable detergent ingredients. All such compositions can be combined in a mixing tank with a single agitator prior to or during wash step 1 of fabric laundering without significantly compromising cleaning performance while still providing excellent fabric conditioning. Add them in the order shown above. Before adding the calcium formate, the pH of the mix is lowered to below 9.0 by adding 0.04 parts of citric acid. The clay slurry shown in step 2 is prepared by mixing the clay into water with a stirrer. Add this clay slurry (Step 2) immediately to the ingredients from Step 1. This formulation intermediate was then passed through a Galarin homogenizer for 6000 ps.
One pass is performed at a pressure of i g and a shear rate of 150,000 s-1. This processing step is critical to activating the clay as an effective suspending agent. Product preparation continues in step 3 by adding the ingredients listed in the order listed above to the processed formulation intermediate through a homogenizer. Mix the ingredients by hand at this point. Finally, add the prills described in step 4 and mix by hand, followed by mechanical stirring for less than 1 minute.

Stable single phase heavy duty fluids are 70″F (21
, 1'C) with a viscosity of 480 cps SpH 9.1 and a yield value of about 146 dynes/C-.

Applicant's agent: Mr. Sato

Claims (1)

[Scope of Claims] 1. A liquid detergent composition comprising a liquid base and having a pH of 5 to 10, further comprising (a) a surfactant component (the surfactant component being an alkyl sulfate, an average of ．．
a surfactant selected from the group consisting of an alkyl ethoxylated sulfate having less than 0, preferably less than 3.0 ethoxylate groups, and a mixture of an alkyl sulfate and an alkyl ethoxylated sulfate, said mixture containing said surfactant. with an average of less than 4.0, preferably less than 3.0 ethoxylate groups per molecule)5.
and (b) water-insoluble conditioning particles having an average diameter of 10μ to 500μ [such particles have the formula: ▲mathematical formula, chemical formula, table, etc.▼ (wherein each R_1 and R_2 is independently
~C_2_0 alkyl or alkenyl, and each R_
3 is H or CH_3, A is an alkyl sulfonate, an arylsulfonate, an alkylaryl sulfonate, an alkyl sulfate, a dialkyl sulfosuccinate, an alkyloxybenzene sulfonate, an acyl isethionate, an acylalkyl taurate, an alkyl ethoxylated sulfate, and an amine-organic anion ion pair complex having an organic anion selected from the group consisting of olefin sulfonates and a mixture of said ion pair complexes] from 0.1% to 20%. Liquid detergent composition. 2. The conditioning particles have a formula of 5% to 95% of the amine-organic anion ion pair conjugate based on the total particle weight and a formula of 95% to 5% based on the total particle weight: ▲ Numerical formula, chemical formula, table, etc. Yes▼ (Each R_1 and R_2 are independently C_1_2 to C_
2_0 alkyl or alkenyl, each R_3 is H
or CH_3, B is an inorganic anion selected from the group consisting of nitrate, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, and dihydrogen phosphate, and x
is an integer from 1 to 3. 3. The liquid detergent composition according to claim 1 or 2, wherein the surfactant has a C_1_2 to C_1_6 alkyl or hydroxyalkyl group. 4. The liquid detergent composition according to claim 1, 2 or 3, wherein the organic anion is a benzene sulfonate or a C_1-C_2_0 linear alkylbenzene sulfonate, preferably a C_1-C_1_3 linear alkylbenzene sulfonate. 5. The composition further includes a detersive builder component, and the detersive builder component is preferably C_1_0 to C_1.
_8 The liquid detergent according to claim 1, 2, 3, or 4, comprising one or more builders selected from the group consisting of alkyl or alkenyl monocarboxylic acids, polycarboxylic acids, polymer carboxylates, and alkenyl succinates. Composition. 6. The liquid detergent composition according to claim 1, 2, 3, 4, or 5, wherein the liquid base consists of water and at least one polar solvent selected from the group consisting of monohydric alcohols and polyols. 7. Anionic surfactants excluding alkyl sulfates and alkyl ethoxylated sulfates, and one or more additional surfactants selected from the group consisting of nonionic surfactants. 7. The liquid detergent composition according to 4, 5, or 6. 8. The composition contains the surfactant component (a) about 7.0
% to about 25%.
or 7. The liquid detergent composition according to 7.